Asymmetric Synthesis of Complex Molecules Using Polyfunctional Cyclopropanes

在这个由化学部化学合成项目资助的项目中，Andrew Harned教授正在开发新的合成方法，该方法基于一系列独特的小分子所表现出的不寻常的反应性。除了探索这些小分子环丙烷的反应性外，人们还在开发新的催化剂来合成这些材料的单一立体异构体。几种具有生物活性的天然产物正在使用这种方法合成。除了这些实验室工作之外，从这项工作中选择的数据正在用于填充基于网络的核磁共振FID数据库，该数据库也正在PI实验室开发中。这种独特的教育资源正被提供给世界各地的教师。该项目的化学重点是开发有效合成复杂分子的新方法。主要目标是利用不寻常的反应模式固有的一个家族的高度功能化，三环环丙烷。这些化合物与亲核试剂或亲电试剂反应可得到高度功能化的开环产物，具有高区域选择性和立体选择性。用新型手性碘化芳基催化剂合成了环丙烷所需的对映富对喹啉。在这些方法学研究的同时，独特的环丙烷被用作构建几种天然产物的关键中间体，特别是氮唑啉内酯和briarane二萜。

In this project funded by the Chemical Synthesis program of the Chemistry Division, Professor Andrew Harned is developing new synthetic methodologies based on the unusual reactivity displayed by a family of unique small molecules. In addition to exploring the reactivity of these small-molecule cyclopropanes, new catalysts are being developed to synthesize these materials as single stereoisomers. Several biologically active natural products are being synthesized using this methodology. In addition to these laboratory efforts, selected data from this work are being used to populate a web-based NMR FID database that is also under development in the PI's laboratory. This unique educational resource is being made available to instructors around the world.The chemical focus of the project concerns the development of new methodology for the efficient synthesis of complex molecules. The main goal is to harness the unusual reactivity patterns inherent to a family of highly functionalized, tricyclic cyclopropanes. Reacting these compounds with either nucleophiles or electrophiles affords highly functionalized, ring-opened products with high regio- and stereoselectivity. The requisite starting materials for the cyclopropanes, enantioenriched para-quinols, are synthesized with new chiral aryl iodide catalysts. Concurrent with these methodology studies, the unique cyclopropanes are being used as key intermediates for the construction of several natural products, specifically azaphilone lactones and briarane diterpenoids.